Process for the production of cineol



Patented Mar, 12, 1935 umrso States v p, 1,994,131 7 raoonss ronrnnjraonuc'rron or omno Clarence GreiderQElev-eland, Ohio, assignor toHercules Powder Cempany, WilmingtomDeL, a

cerporation cf Delaware No Drawing; Application March 1-9, 1932,

- Serial No. 600,071

10 Claims. (01. 250-4153) My inventicn relates to a method. for theproduction of cineol by the treatment of pine oil and to theproductionof a solvent for treatment of pine oil. r

Pine oil, usually produced by steamdistillation of pine stump wood, isknown to be a complex mixture of diiierent substances. It, however,contains essentially the high boiling alcohols, terpineol, fenchylalcohol and borneol. Pine oil itself has little or no colloiding orsolvent action upon nitrocellulose and its individual constituentslikewise possess little colloiding power. However, I' have discoveredthat if pine oil be treated with a substantially concentrated acid underthe prop or temperature conditions, its constituent terpineol may beconverted into cineol with the production of a nitrocellulose solvent ofsubstantial value.

Further, I have discovered that if pine oil, prior to its treatment withacid, be oxidized for the production of camphor and fenchone from itsconstituents borneol and ,ienchyl alcohol, as, for example, inaccordance with the process described in the application for patent ofIrvin W. Humphrey, filed November 22, 1924, Serial No. 751,682, anitrocellulose solvent of a high degree of eficiency will be obtained.

Having now indicated, in a general way, the nature and purpose of myinvention, I will proceed to a more detailed description thereof.

For the production. of cineol as a solvent for nitrocellulose from, forexample, pine oil, there is added to the pine oil an acid, which may beorganic or inorganic, for example, sulphuric acid, phosphoric acid, oroxalic acid, or the like, in an amount preferably equal in volume to thevolume of pine oil, but which may be varied from an amount in volumeone-half of the volume of the pine oil to an amount in volume in excessof the volume of the pine oil. The acid should be of substantialconcentration, preferably a 44% by weight (39% by volume), but theconcentration may range from 30%-50'% by weight (20%-l0% by volume) withsatisfactory results.

After the addition of the acid to the pine oil, 7

it should be stirred vigorously with the application of heat. Forexample, vigorous stirring for a period of six hours at a temperature offorty degrees C. will suffice, though the length of the stirring periodmay be increased or decreased by a decrease or increase of thetemperature, while the temperature may be varied considerably with theconcentration of acid used.

nitrocellulose which includes cineol as a constituent by the it may benoted that While the'temperature used in carrying out the process may bewidely varied'under varying conditions, as, for example, ofacidconcentration, pressure, etc the use of a temperature at which anysubstantial dehydration of terpineol effected; i. e. a breaking downinto terpenes and water, willbe avoided, itbeing understood that thecineol is formed by molecular rearrangement of the terpineol withoutloss of water. Thus by way of illustration and not where a relativelyconcentrated acid is used and the process carried'out under atmosphericpressure a temperature within, for example, therange it- C. will befound to be satisfactory. f

The addition of the acid to the pine oil, with 1' v the application ofheat and stirring, results in a rearrangement of the terpineol, having aboiling point about 218 C., and similar alcohol constituents of the pineoil to form cineol, having a boiling range of about 175 nitrocellulosesolvents range.

After the requisite stirring of the pine oil and acid to eiiect theproduction of cineol from the having a similar boiling terpineolconstituent of the pine oil, it is sepa- 2 rated, washed with an alkalisolution to neutralize any acid remaining, and finally steam distilledin the usual manner.

In the carrying out of the process, for the production of cineol as anitrocellulose solvent, 30

the pine oil may be oxidized for the production of camphor and fenchonebefore treatment with an acid.

To the pine oil, which, as has been indicated, contains, in addition toterpineol cohols, bornecl and fenchyl alcohol, there is added anoxidizing agent, comprising, for example, sodium bichromate, sulphuricacid and water. The pine oil and oxidizing agent are stirred and cooled.The oxidized pine oil,

the oxidation process, as well as terpineol, is then treated with acid,as above described, for the production of cineol from the. terpineolconstituent.

As' an example of a satisfactory formula for the oxidation of pine oil,there may be added to 100 grams of pine oil a mixture composed, forexample, of 20 grams sodium bichromate, 30 grams of concentratedsulphuric acid and. grams of water, with treatment as above described. vI

As a result of my invention, there is provided a valuable solvent fornitrocellulose and a simple and inexpensive method of producing the samewill "be ti by way of limitation 1U C.-l'77 C. and probably other 20 andsimilar al- 35 which contains camphor and fenchone, as a result ofeither from ordinary pine oil or from pine oil which has been oxidizedfor the production of camphor and fenchone as solvents fornitrocellulose. When the process is utilized in connection with oxidizedpine oil, it possesses great advantages of economy, since the amount ofoxidizing agent may be greatly decreased and a solvent of greatlyincreased value over oxidized pine oil is produced.

This application is filed as a continuation in part of an applicationfiled by me November 3, 1925, Serial Number 66,683.

What I claim and desire to protect by Letters Patent is:

1. The method of producing cineol which includes treating pine oilhaving terpineol as a constituent with a mineral acid and at atemperature below that at which substantial dehydration of terpineol wilbe effected.

2. The method of producing cineol which includes treating pine oilhaving terpineol as a constituent with sulphuric acid and at .a .temperature below that at which substantial dehydration of terpineol willbe eifected.

13. The method'o'f 'producing cineol which includes treating pine oilhaving terpineol as a constituent with substantiallyconcentratedrsulphuric acid at a temperature belowlthat at whichsubstantialdehydration of'terpineol will be efiected, for the productionof cineol.

4. The method of producing cineol which includes oxidizing pineoilhaving terpineol as a constituent and treating the oxidized pine oilwith a'mineral acid and at a temperature below that at whichsubstantial'dehydration of terpineol will be effected; for theproduction of cineol.

5. The method of producing cineol which inpineol wil be effected to beefiected, for the production of cineol..

cludes treating pine oil having terpineol as a mineral acid and at atemperature below that at which substantial dehydration of terpineolwill be efiected.

6. The method of producing cineol which includes oxidizing pine oilhaving terpineol as a constituent and treating the' oxidized pine oilwith sulphuric acid and at a'temperature below that at which substantialdehydration of tereifect the productionof cineol.

7 The method of producing cineol which includes treating pine oil-havingterpineol as a constituent with sulphuric acid of -50% concentration at'a temperature of the order of 74040" c. v

8. The method of producing cineol which includes treating pine oilhaving terpineol as a constituent with sulphuric acid of 30-50%concentration and at a temperature below that at which substantialdehydration of terpineol will 9. The method of producing cineol whichincludes treating pine oil having terpineol as a constituent withphosphoric acid and at a temperature below thatat'which substantialdehydration of terpineol will be efiected, for the production of cineol.p

10. The method of producing cineol which in cludes oxidizing pineoilhaving terpineol-as a constituent and treating the oxidized pine oilwith phosphoric acid and production of cineol.

be effected, for the v V i Y CLARENCE E GREIDER,

at a temperature below'that V at which substantial dehydration ofterpineol will

